Fuel Additives for Use in High Level Alcohol-Gasoline Blends

ABSTRACT

The present invention provides a fuel additive concentrate comprising a polyetheramine, antioxidant; and a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof. Additionally, the present invention further provides for a fuel composition comprising a fuel which is a liquid at room temperature; and additive, wherein the additive is selected from the group consisting of: a polyetheramine; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof.

BACKGROUND OF THE INVENTION

The present invention relates to fuel additive concentrate, the fueladditive concentrate in an ethanol-gasoline blended fuel and the methodfor fueling an internal combustion engine, providing improved fueleconomy and retention of fuel economy, deposit control, oxidationcontrol, and wear and friction reduction.

Governments around the world are implementing the use of oxygenates ingasoline for economic and environmental reasons. Ethanol in particularis gaining ground as the oxygenate of choice as it presents a renewableand environmentally friendly alternative to other octane boosters, suchas, tetra ethyl lead (TEL) and methyl tert-butyl ether (MTBE).Additionally, ethanol benefits the agricultural sector and therefore,has the backing of political and pricing support. This in combinationwith rises in crude oil, desire for energy independence, and fears ofglobal warming explains the recent growth in the ethanol energy market.In the United States, ethanol has been available since the late 1970'sand is added at 10% (E10) to approximately one-third of all gasolineused in North America. The production of ethanol blended fuels has begunin Europe with Spain and Sweden at the forefront. Brazil has a longhistory of using ethanol and ethanol blends. Other countries in LatinAmerica have varied but growing levels of E10. In the Asia Pacificregion, Thailand has lead the way and E10 is widely available. Othercountries with regional (but not national) mandates include China andIndia while Japan, Australia and the Philippines are not far behind.

Ethanol blended gasoline have a long history and are widely understoodto present certain technical challenges which have been successfullyaddressed in most cases. New markets will likely face the traditionalissues associated with ethanol blended gasoline, such as, the tendencyfor increased deposits formation, fuel system corrosion, loss of fueleconomy and, an increase in inlet valve sticking. In most cases,formulation adjustments and/or increases in additive level is theremedy, but new high level ethanol blended gasoline (>50% Ethanol−E50 orgreater) has entered the marketplace and may present new challenges.Some issues have been addressed through the development of new vehicletechnology, while other issue will require new inventive additivestechnology.

The present invention, therefore, solves the problem of ethanol-gasolineblend fuels tendency for engine deposits formation, lubricant oxidation,and a loss of fuel economy by providing fuel additives to theethanol-gasoline blends that prevent engine deposits, slows lubricantoxidation and improves fuel economy.

SUMMARY OF THE INVENTION

The present invention provides a fuel additive concentrate comprising:

-   -   a. polyetheramine;    -   b. antioxidant; and    -   c. a friction modifier selected from the group consisting of an        alkoxylated fatty amine, a fatty acid or derivative thereof, and        mixture thereof.

The present invention further provides for a fuel compositioncomprising:

-   -   a. a fuel which is a liquid at room temperature; and    -   b. additive

wherein the additive is selected from the group consisting of: apolyetheramine; antioxidant; friction modifier selected from the groupconsisting of an alkoxylated fatty amine, a fatty acid or derivativethereof, and mixture thereof; and mixtures thereof.

The present invention further provides a method for fueling an internalcombustion engine, comprising:

A. supplying to an internal combustion engine:

-   -   i. a fuel which is a liquid at room temperature;    -   ii. polyetheramine;    -   iii. antioxidant; and    -   iv. a friction modifier selected from the group consisting of an        alkoxylated fatty amine, a fatty acid or derivative thereof, and        mixture thereof.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

FIELD OF THE INVENTION

This invention involves fuel additive concentrate that includes: apolyetheramine, antioxidant, and a friction modifier selected the groupconsisting of an alkoxylated fatty amine, a fatty acid or derivativethereof, and mixture thereof; a fuel composition that includes a fuelwhich is a liquid at room temperature and an additive wherein theadditive is selected from the group consisting of: a polyetheramine;antioxidant; friction modifier selected from the group consisting of analkoxylated fatty amine, a fatty acid or derivative thereof, and mixturethereof; and mixtures thereof, and a method of operating an internalcombustion engine with the fuel composition. The concentrates,compositions and methods of the present invention promote enginecleanliness and fuel economy, while controlling lubricant oxidation,which enables optimal engine operation.

Fuel

The fuel composition of the present invention can comprise the fueladditive concentrate, as described above, and a fuel which is a liquidat room temperature and is useful in fueling an engine. The fuel isnormally a liquid at ambient conditions e.g., room temperature (20 to30° C.). The fuel can be a hydrocarbon fuel, a nonhydrocarbon fuel, or amixture thereof. The hydrocarbon fuel can be a petroleum distillate toinclude a gasoline as defined by ASTM specification D4814 or a dieselfuel as defined by ASTM specification D975. In an embodiment of theinvention, the fuel is a gasoline, and in other embodiment, the fuel isa leaded gasoline, or a nonleaded gasoline. In another embodiment ofthis invention, the fuel is a diesel fuel. The hydrocarbon fuel can be ahydrocarbon prepared by a gas to liquid process to include, for example,hydrocarbons prepared by a process, such as, the Fischer-Tropschprocess. The nonhydrocarbon fuel can be an oxygen containingcomposition, often referred to as an oxygenate, which can include analcohol, an ether, a ketone, an ester of a carboxylic acid, anitroalkane, or a mixture thereof. The nonhydrocarbon fuel can include,for example, methanol, ethanol, propanol, butanol, methyl t-butyl ether,methyl ethyl ketone, transesterified oils and/or fats from plants andanimals such as rapeseed methyl ester and soybean methyl ester, andnitromethane. In several embodiments of this invention, the fuel canhave an oxygenate content on a weight basis that is 15 percent byweight, or 25 percent by weight, or 50 percent by weight, or 65 percentby weight, or 85 percent by weight, or 90 percent by weight. Mixtures ofhydrocarbon and nonhydrocarbon fuels can include, for example, gasolineand methanol and/or ethanol, diesel fuel and ethanol, and diesel fueland a transesterified plant oil such as rapeseed methyl ester, fuelsreferred to as E85 or M85, fuels referred to as AlCool™. In oneembodiment, mixtures of hydrocarbon and nonhydrocarbon fuels can bedefined by ASTM D-5798-99. In several embodiments of this invention, themixtures of hydrocarbon and nonhydrocarbon fuels can have an oxygenatecontent on a weight basis that is 15 percent by weight, or 25 percent byweight, or 50 percent by weight, or 65 percent by weight, or 85 percentby weight, or 90 by weight. In another embodiment, the fuel comprises ablend of ethanol and gasoline having a ratio from 25:75 to 90:10. In anembodiment of the invention, the fuel can be an emulsion of water in ahydrocarbon fuel, a nonhydrocarbon fuel, or a mixture thereof. Inseveral embodiments of this invention, the fuel can have a sulfurcontent on a weight basis that is 5000 ppm or less, 1000 ppm or less,300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less. Inanother embodiment, the fuel can have a sulfur content on a weight basisof 1 to 100 ppm. In one embodiment, the fuel contains 0 ppm to 1000 ppm,or 0 to 500 ppm, or 0 to 100 ppm, or 0 to 50 ppm, or 0 to 25 ppm, or 0to 10 ppm, or 0 to 5 ppm of alkali metals, alkaline earth metals,transition metals or mixtures thereof. In another embodiment, the fuelcontains 1 to 10 ppm by weight of alkali metals, alkaline earth metals,transition metals or mixtures thereof. It is well known in the art thata fuel containing alkali metals, alkaline earth metals, transitionmetals or mixtures thereof have a greater tendency to form deposits andtherefore foul or plug injectors. The fuel of the invention can bepresent in a fuel composition in a major amount that is generallygreater than 50 percent by weight, and in other embodiments is presentat greater than 90 percent by weight, greater than 95 percent by weight,greater than 99.5 percent by weight, or greater than 99.8 percent byweight.

Polyetheramine

Polyetheramines of this invention include compounds having two or moreconsecutive ether groups and at least one primary, secondary or tertiaryamine group where the amine nitrogen has some basicity. Thepolyetheramines of this invention include poly(oxyalkylene)amines havinga sufficient number of repeating oxyalkylene units to render thepoly(oxyalkylene)amine soluble in a normally liquid fuel, such as, inhydrocarbons boiling in a gasoline or diesel fuel range and blends ofhydrocarbon fuel with non-hydrocarbon fuel. Generally,poly(oxyalkylene)amines having at least about 5 oxyalkylene units aresuitable for use in the present invention. Poly(oxyalkylene)amines caninclude: hydrocarbylpoly(oxyalkylene)amines,hydrocarbylpoly(oxyalkylene)polyamines, hydropoly(oxyalkylene)amines,hydropoly(oxyalkylene)polyamines, and derivatives of polyhydric alcoholshaving at least two poly(oxyalkylene)amine and/orpoly(oxyalkylene)polyamine chains on the molecule of the derivative. Inone embodiment, the poly(oxyalkylene)amine for use in the invention isrepresented by the formula RO(AO)mR1NR2R3 (I) wherein R is a hydrocarbylgroup of 1 to 50 carbon atoms, or about 8 to about 30 carbon atoms; A isan alkylene group having 2 to 18 carbon atoms and preferably 2 to 6carbon atoms; m is a number from 1 to about 50; R1 is an alkylene grouphaving 2 to 18 carbon atoms or preferably 2 to 6 carbon atoms; and R2and R3 are independently hydrogen, a hydrocarbyl group or —[R4N(R5)]nR6wherein R4 is an alkylene group having 2 to 6 carbon atoms, R5 and R6are independently hydrogen or a hydrocarbyl group, and n is a numberfrom 1 to 7.

In another embodiment, the poly(oxyalkylene)amine of the presentinvention can be represented by the formula:RO[CH2CH(CH2CH3)O]mCH2CH2CH2NH2 (II) wherein R is an aliphatic group oralkyl-substituted phenyl group of about 8 to about 30 carbon atoms; andm is a number from about 12 to about 30. In yet another embodiment, thepoly(oxyalkylene)amine of the present invention can be represented bythe formula:CH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2O—[CH2CH(CH2CH3)O]mCH2CH2CH2NH2(III) wherein m is a number from about 16 to about 28.Poly(oxyalkylene)amines of the present invention can have a molecularweight in the range from about 300 to about 5,000.

The polyetheramines of the present invention can be prepared byinitially condensing an alcohol or alkylphenol with an alkylene oxide,mixture of alkylene oxides or with several alkylene oxides in sequentialfashion in a 1:1-50 mole ratio of hydric compound to alkylene oxide toform a polyether intermediate. U.S. Pat. Nos. 5,112,364 and 5,264,006provide reaction conditions for preparing a polyether intermediate.

The alcohol can be monohydric or polyhydric, linear or branched,saturated or unsaturated and having 1 to 50 carbon atoms, or from 8 to30 carbon atoms, or from 10 to 16 carbon atoms. Branched alcohols of thepresent invention can include Guerbet alcohols, as described in U.S.Pat. No. 5,264,006, which generally contain between 12 and 40 carbonatoms and can be represented by the formula RCH(CH2CH2R)CH2OH (IV) whereR is a hydrocarbyl group. In one embodiment, the alkyl group of thealkylphenols can be 1 to 50 carbon atoms, or 2 to 24 carbon atoms, or 10to 20 carbon atoms.

In one embodiment, the alkylene oxides include 1,2-epoxyalkanes having 2to about 18 carbon atoms, or 2 to about 6 carbon atoms. In yet anotherembodiment, the alkylene oxides can be ethylene oxide, propylene oxideand butylene oxide. Especially useful is propylene oxide, butyleneoxide, or a mixture thereof. The number of alkylene oxide units in thepolyether intermediate can be 1-50, or 12-30, or 16-28.

The polyether intermediates can be converted to polyetheramines byseveral methods. The polyether intermediate can be converted to apolyetheramine by a reductive amination with ammonia, a primary amine ora polyamine as described in U.S. Pat. Nos. 5,112,364 and 5,752,991. Inone embodiment, the polyether intermediate can be converted to apolyetheramine via an addition reaction of the polyether toacrylonitrile to form a nitrile which is then hydrogenated to form thepolyetheramine. U.S. Pat. No. 5,264,006 provides reaction conditions forthe cyanoethylation of the polyether with acrylonitrile and thesubsequent hydrogenation to form the polyetheramine. In yet anotherembodiment, the polyether intermediate or poly(oxyalkylene) alcohol isconverted to the corresponding poly(oxyalkylene) chloride via a suitablechlorinating agent followed by displacement of chlorine with ammonia, aprimary or secondary amine, or a polyamine as described in U.S. Pat. No.4,247,301.

In one embodiment, the polyetheramine in the fuel composition may bepresent in an amount from about 1 to about 10000 ppm, or about 5 toabout 5000, or about 20 to about 4000 or about 40 to about 3500 ppm.

In one embodiment, the polyetheramine can be present in the fueladditive concentration in an amount from about 1 to about 99 percent byweight, or about 10 to about 80 percent by weight, about 20 to about 60percent by weight and about 20 to about 50 percent by weight.

Friction Modifier

The fuel additive concentrate of the present invention can comprise afriction modifier. The friction modifier can be selected from the groupconsisting of an alkoxyalted fatty amine, fatty acid or derivativethereof, and mixtures thereof.

Alkoxylated Fatty Amine

The alkoxylated fatty amine of the present invention can include aminesrepresented by the formula:

wherein R is a hydrocarbyl group having about 4 to 30 carbon atoms, A¹and A² are vicinal alkylene groups, and the sum of x and y is an integerthat is at least 1. The hydrocarbyl group is a univalent radical ofcarbon atoms that is predominantly hydrocarbon in nature, but can havenonhydrocarbon substituent groups and can have heteroatoms. Thehydrocarbyl group R can be an alkyl or alkylene group of about 4 to 30carbon atoms, or about 10 to 22 carbon atoms. The vicinal alkylenegroups A¹ and A² can be the same or different and include:ethylene(—CH2CH2—), propylene (—CH2CH2CH2—) and butylene(—CH2CH2CH2CH2—) having the carbon to nitrogen and carbon to oxygenbonds on adjacent or neighboring carbon atoms. Examples of alkoxylatedfatty amines can include: diethoxylated tallowamine, diethoxylatedoleylamine, diethoxylated stearylamine, and the diethoxylated amine fromsoybean oil fatty acids. Alkoxylated fatty amines are commerciallyavailable from Akzo under the Ethomeen® series.

Fatty Acid or Derivative Thereof

In one embodiment, the fatty acid or derivative thereof can have about 4to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms.Saturated and unsaturated monocarboxylic acids are useful and includecapric, lauric, myristic, palmitic, stearic, behenic, oleic,petroselinic, elaidic, palmitoleic, linoleic, linolenic and erucic acid.Typical fatty acids are those derived from natural oil typicallycontaining C6 or C22 fatty acid esters, i.e., glycerol fatty acid estersor triglycerides derived from natural sources, for use herein include,but are not limited to beef tallow oil, lard oil, palm oil, castor oil,cottonseed oil, corn oil, peanut oil, soybean oil, sunflower oil, oliveoil, whale oil, coconut oil, palm oil, rape oil, and soya oil.

In another embodiment of this invention, the fatty acid can be thepartial ester of a fatty carboxylic acid. The partial ester of thepresent invention has at least one free hydroxyl group and is formed byreacting at least one fatty carboxylic acid and at least one polyhydricalcohol.

The fatty carboxylic acid used to form the partial ester can besaturated or unsaturated aliphatic, can be branched or straight chain,can be a monocarboxylic or polycarboxylic acid, and can be a single acidor mixture of acids. The fatty carboxylic acid can have about 4 to 30carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms.Saturated and unsaturated monocarboxylic acids are useful and include,for example, capric, lauric, myristic, palmitic, stearic, behenic,oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic anderucic acid.

The polyhydric alcohol used to form the partial ester has two or morehydroxyl groups and includes alkylene glycols, polyalkylene glycols,triols, polyols having more than three hydroxyl groups, and mixturesthereof. Examples of polyhydric alcohols include ethylene glycol,diethylene glycol, neopentyl glycol, glycerol, trimethylol propane,pentaerythritol, and sorbitol.

The partial esters having at least one free hydroxyl group arecommercially available or can be formed by a variety of methods wellknown in the art. These esters are derived from any of the abovedescribed fatty carboxylic acids and polyhydric alcohols or mixturesthereof. Preferred esters are derived from fatty carboxylic acids havingabout 12 to 22 carbon atoms and glycerol, and will usually be mixturesof mono- and diglycerides, such as, a mixture of glycerol monooleate andglycerol dioleate. In one embodiment, the friction modifier of thepresent invention is glycerol monoleate.

Another derivative of the fatty carboxylic acid is the amide of thefatty carboxylic acid. In general, these compounds are the reactionproduct of the natural fatty acid oils containing 6 to 22 carbon atomsand an amine. The fatty carboxylic acid of these amides can be saturatedor unsaturated aliphatic, can be branched or straight chain, can be amonocarboxylic or polycarboxylic acid, and can be a single acid ormixture of acids. The fatty carboxylic acid can have about 4 to 30carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms.Saturated and unsaturated monocarboxylic acids are useful and include,for example, capric, lauric, myristic, palmitic, stearic, behenic,oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic anderucic acid.

The amine can be an alkyl amine having from about 2 to about 10 carbonatoms, or about 4 to about 6 carbon atoms. A typical amine can be thealkanol amines. The alkanolamine used in the reaction with the fattyacid can be a primary or secondary amine, which possesses at least onehydroxy group. The alkanolamine corresponds to the general formulaHN(R1OH)2-xHx wherein R1 is a lower hydrocarbyl having from about two toabout six carbon atoms and x is 0 or 1. The expression “alkanolamine” isused in its broadest sense to include compounds containing at least oneprimary or secondary amine and at least one hydroxy group, such as, forexample, monoalkanolamines, dialkanolamines, and so forth. It isbelieved that almost any alkanolamine can be used, although preferredalkanolamines are lower alkanolamines having form about two to about sixcarbon atoms. The alkanolamine can possess an O or N functionality, inaddition to the one amino group (that group being a primary of secondaryamino group), and at least one hydroxy group. Suitable alkanolamines foruse herein include: monoethanolamine, diethanolamine, propanolamine,isopropanolamine, dipropanolamine, di-isopropanolamine, butanolamines,aminoethylaminoethanols, e.g., 2-(2-aminoethoamino)ethanol, and the likewith diethanolamine being preferred. It is also contemplated thatmixtures of two or more alkanolamines can be employed.

In one embodiment, the friction modifier can be present in the fueladditive concentrate in an amount from about 1 to about 99 percent byweight, or about 2 to about 50 percent by weight, or about 5 to about 40percent by weight, or about 5 to about 30 percent by weight, in yetanother embodiment from about 8 to about 25 percent by weight.

In one embodiment, the friction modifier of this invention can bepresent in a fuel composition on a weight basis from about 1 to about10,000 ppm (parts per million), and in other embodiment from about 5 toabout 8,000 ppm, or about 10 to about 7000 ppm, or about 20 to about5000 ppm, or about 30 to about 2000 ppm, or about 50 to about 1500, orabout 40 to about 1000 ppm, or about 40 to about 650 ppm.

Antioxidant

The present invention also includes one or more antioxidants. Theantioxidants for use in the present invention are well known and includea variety of chemical types including phenate sulfides,phosphosulfurized terpenes, sulfurized esters, aromatic amines, andhindered phenols.

Aromatic amines are typically of the formula

wherein R⁵ is a phenyl group or a phenyl group substituted by R⁷, and R⁶and R⁷ are independently a hydrogen or an alkyl group containing 1 to 24carbon atoms. Preferably R⁵ is a phenyl group substituted by R⁷ and R⁶and R⁷ are alkyl groups containing from 4 to 20 carbon atoms. In oneembodiment, the antioxidant can be an alkylated diphenylamine, such as,nonylated diphenylamine containing typically some of the formula

Hindered phenol antioxidants are typically alkyl phenols of the formula

wherein R⁴ is an alkyl group containing 1 to 24 carbon atoms and m is aninteger of 1 to 5. In certain embodiments, R contains 4 to 18 carbonatoms or 4 to 12 carbon atoms. R⁴ may be either straight chained orbranched chained, especially branched. Suitable values of m include 1 to4, such as 1 to 3 or, particularly, 2. In certain well-knownembodiments, the phenol is a butyl substituted phenol containing 2 or 3t-butyl groups. When a is 2, the t-butyl groups may occupy the2,6-positions, that is, the phenol is sterically hindered:

The antioxidant can be, and typically is, further substituted at the4-position with any of a number of substituents, such as hydrocarbylgroups or groups bridging to another hindered phenolic ring.

Also included among the antioxidants are hindered ester substitutedphenols such as those represented by the formula:

wherein t-alkyl can be, among others, t-butyl, R³ is a straight chain orbranched chain alkyl group containing about 1 to about 22 carbon atoms,or about 2 to about 22, or about 2 to about 8, or about 4 to about 8carbon atoms. R³ may be a 2-ethylhexyl group or an n-butyl or n-octylgroup. Hindered ester substituted phenols can be prepared by heating a2,6-dialkylphenol with an acrylate ester under base catalysisconditions, such as, aqueous KOH.

The antioxidants of the present invention can also include sulfurizedolefins, such as, mono-, or disulfides or mixtures thereof. Thesematerials generally have sulfide linkages having 1 to 10 sulfur atoms,or 1 to 4, or 1 or 2 sulfur atoms. Materials, which can be sulfurized toform the sulfurized organic compositions of the present invention,include: oils, fatty acids and esters, olefins and polyolefins madethereof, terpenes, or Diels-Alder adducts. Details of methods ofpreparing some such sulfurized materials can be found in U.S. Pat. Nos.3,471,404 and 4,191,659. Molybdenum compounds can also serve asantioxidants. The use of molybdenum and sulfur containing compositionsas antioxidants is known.

In certain embodiment, a mixture of antioxidants are employed, such as,both a phenolic and an aromatic amine antioxidant, or mixtures thereof,or alternatively phenolic, or aromatic amine, or phosphosulfurizedolefin antioxidants or molybdenum antioxidant or mixtures thereof.

In one embodiment, the amount of the antioxidant in the fuel compositioncan be present in an amount from about 1 to about 1000 ppm, or about 1to about 5000, or about 2 to about 500, or about 4 to about 200 or about5 to about 100 ppm.

In one embodiment, the amount of antioxidant can be present in the fueladditive concentration in an amount from about 1 to about 99 percent byweight, or from about 1 to about 40 percent by weight, or from about 2to about 30 percent by weight, or from about 2 to about 20 percent byweight.

Fuel Composition

In one embodiment, the fuel composition contains a fuel, which is aliquid at room temperature, and an additive wherein the additive isselected from the group consisting of: a polyetheramine; antioxidant;friction modifier selected from the group consisting of an alkoxylatedfatty amine, a fatty acid or derivative thereof, and mixture thereof;and mixtures thereof. The fuel, which is a liquid at room temperature,and additives of the fuel composition are described above.

Fuel Additive Concentrate

In one embodiment, the fuel additive concentrate of the presentinvention can be present in a fuel composition in an amount from about 1to about 10000 ppm, in another embodiment about 5 to about 8000 ppm, inanother embodiment about 10 to about 5000 ppm or about 20 to about 5000ppm, in yet another embodiment about 100 to about 4000 ppm, and inanother embodiment about 200 to about 2000, or about 300 to about 2000or about 300 to about 1000 ppm.

Miscellaneous

The fuel additive concentrate compositions and fuel compositions of thepresent invention can contain other additives that are well known tothose of skill in the art. These can include anti-knock agents such astetra-alkyl lead compounds and MMT (methylcyclopentadienyl manganesetricarbonyl), lead scavengers such as halo-alkanes, corrosioninhibitors, dyes, bacteriostatic agents, auxiliary, gum inhibitors,marking agents, metal deactivators, detergents, demulsifiers, ormixtures thereof. The fuel compositions of this invention can belead-containing or lead-free fuels.

INDUSTRIAL APPLICATION

In one embodiment the invention is useful for a liquid fuel or for aninternal combustion engine. The internal combustion engine includes a2-stroke or 4-stroke engine fuelled with gasoline, diesel, a natural gasor a mixed gasoline/alcohol. The diesel engine includes both light dutyand heavy duty diesel engines. The gasoline engine includes a directinjection gasoline engine.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form aring); substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of” permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

1. A fuel additive concentrate comprising: a. polyetheramine; b.antioxidant; and c. a friction modifier selected from the groupconsisting of an alkoxylated fatty amine, a fatty acid or derivativethereof, and mixture thereof.
 2. The fuel additive concentrate of claim1, wherein the polyethermamine is represented by the formulaRO(AO)_(m)R¹NR²R³; wherein R is a hydrocarbyl group of about 8 to about30 carbon atoms; A is an alkylene group having 2 to 6 carbon atoms; m isa number from 1 to about 50; R¹ is an alkylene group having 2 to 6carbon atoms; and R² and R³ are independently hydrogen, a hydrocarbylgroup or —[R⁴N(R⁵)]_(n)R⁶ wherein R⁴ is an alkylene group having 2 to 6carbon atoms, R⁵ and R⁶ are independently hydrogen or a hydrocarbylgroup, and n is a number from 1 to
 7. 3. The fuel additive concentrateof claim 2, wherein the polyetheramine is represented by the formulaRO[CH₂CH(CH₂CH₃)O]_(m)CH₂CH₂CH₂NH₂; wherein R is an aliphatic group oralkyl-substituted phenyl group of about 8 to about 30 carbon atoms; andm is a number from about 12 to about
 30. 4. The fuel additiveconcentrate of claim 3, wherein the polyetheramine is represented by theformulaCH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2O[CH2CH(CH2CH3)O]mCH2CH2CH2NH2;wherein m is a number from about 16 to about
 28. 5. The fuel additiveconcentrate of claim 1, wherein the antioxidant is selected from thegroup consisting of hindered phenol or derivatives thereof, hinderedamines or derivatives thereof, and mixtures thereof.
 6. The frictionmodifier of claim 1, wherein the friction modifier is glycerolmonooleate.
 7. A fuel composition comprising: a. a fuel which is aliquid at room temperature; and b. additive wherein the additive isselected from the group consisting of: a polyetheramine; antioxidant;friction modifier selected from the group consisting of an alkoxylatedfatty amine, a fatty acid or derivative thereof, and mixture thereof;and mixtures thereof.
 8. The fuel composition of claim 7, wherein thefuel comprises a blend of ethanol and gasoline having a ratio from 25:75to 90:10.
 9. A method of fueling an internal combustion enginecomprising: a. supplying to the internal combustion engine: i. a fuelwhich is a liquid at room temperature; ii. polyetheramine; iii.antioxidant; and iv. a friction modifier selected from the groupconsisting of an alkoxylated fatty amine, a fatty acid or derivativethereof, and mixture thereof.